New derivatives of anthanthrone and process of making same



Patented May 19, 1931 UNITE/f STATES RICHARD HERZ, OF FRANKFORT-ON-THEJAIN, AEID'VTERIIER ZERWECK,;OFFEQHEN- HEIM, NEARERANKFOE'E-ON-THEi/IAIN, GERMANY, ASSIGlTORS TO Y-GENERAL I AN'ILINEWORKS, INC., OF NEW YORK, N. Y., A CORPORATION OF DELAWARE i NEWDERIVATIVES OF ANTHANTHRONE AND PROCESS OF MAKING: SAME No Drawing.Application filed Ooto ber 7, 1927, Serial No. 224,755, and iniGerman'yOctober 13,1926.

In U. S. Patent No. 1,646,290 a new process is 'clescribedforniarfufactnring the l-aminonaphl-halenc-8-carboxyhc acld, whichconsis'ts in acting with an alkaline acting agent on the8-cyannaphthalene-1-sulf0nic acid,

ing new derivatives. of anfohanthronc by starting fromnaphthostyril-sulfonic acids,

- obtainable by sulfonating :naphthostyril;

Oui- -process consists in "saponi'fying the naphthostyril sulfonic acids'tov the corre- I naphthostyril sulfonic acids (303E) dilute causticsponding sulfonic acid dcrivatives of 1- aniinonaphthalene-8-carboxylioacid dia'zotizingi thesederivatives, treating-these diazocoinponnclsWith reducing agents, con- 'Vfting the formed sulfonic acid derivativcsof the 1.1- clinaphthyl-8.8-- dicarboxylic acid by alkali fusion intothe corresponding" hydroxyclerivatives, subjecting'these to the actionofacicl condensing agents and treating" finally the formed'hydroXy-anthanthrones with alkylating agents. 7 i

The course of the reaction may be illus bratedbfy the following schemeof formulas NHz alkali solutions sulforlerivatives of l-aminonaphthalenaS-carboxylic acid diazotizing and acting with reducing age'nts)}-- sulfo derivatives of A 1.1-dinaphthy1-8.8-

, dicarboxylic acid hydroxyderivatives of anthanthrone 6 v alkali 3' I(S0311) fusion 1 7 A h 2' AV 1 I 7 '2 hydroxyderivativ es of 1.1-1i11aphthy1-8.8- V dicarboxylic acid acid condensing agents (O-alkyl)alkoxyderivatives of anthanthrone The hydroxyderivatives ofanthanthrone, obtained as the last intermediates of our combinedprocess, are also new compounds. The new alkoxyanthanthrones, obtainedin a pure state with an excellent yield according to our invention andcorresponding probably to the aforesaid formula, are when dry violetpowders, soluble in concentrated sulfuric acid with a greenish color.They form with an alkaline hydrosullite solution a reddish to bluishcolored vat and dye coton therefrom violet shades of a good fastnessespecially to light.

In order to further illustrate our invention the following examplegiven, the parts being by weight and all temperatures in Centigradedegrees. We wish it however to be understood, that we are not limited tothe particular conditions nor to the specific products mentionedthereln.

Ewamp Ze formed corresponds probably to the formula O CNH It isseparated in form of its potassium salt HO O C IIQ'H:

For transforming this acid in the correspondingdinaphthyl-disulfo-dicarboxylic acid, 267 parts of it are diazotized andthe diazocompound is introduced at an ordinary temperatureinto anammonical solution of cuprous oxide, prepared from 500 parts of sulfateof copper by means of sulfur dioxide. The dinaphthyldisulfo-dicarboxylicacid,

separating from the solution by acidifying, corresponds probably to theformula:

HOOC OOH This step of our combined process is covered by U. S. PatentNo. 1,684,272 of Herz and Zerweck, issued Sept. 11, 1928.

1 part of this dinaphthyl-disulfo-dicarboxylic acid is introduced at140450 into a molten mixture of 15 parts of caustic potash and 4: partsof water. The temperature of the mass is slowly increased to 180-190 andkeptfor some time. After cooling down the mass is diluted with water andby acidifying carefully with hydrochloric acid the formeddihydroxy-L1-dinaphthyl 8.8- dicarboxylic acid of the probable formula:

HOOC

is isolated, filtered and washed with icewater. It crystallizes fromwater in colorless crystals.

1 part of this dihydroxydinaphthyl-dicarboxylic acid is boiled for somehours with 10 ,parts of acetic acid anhydride and 1 part of anhydrouszinc chloride in an apparatus provided with a reflux condenser. Aftercooling down the mass the reaction product is filtered and washed withspirit and water. The formed new dihydroxy-anthanthrone correspondingprobably to the formula:

is when dry a brownish red powder, soluble in concentrated sulfuric acidwith a yellowish green color, diflicultly soluble in hot caus:

' tic alkali solutions with a greenish blue color.

The blue color of the mass turnsto violet-red after continuing theheating for some hours the mass is cooled down and the separated compactcrystals are filtered and washed with spirit and water. Thedimethoxyanthanthrone thus obtained corresponds probably to the formula:y

It is when dry a violet powder, soluble in 0011- centrated sulfuric acidwith a yellowish green From a bluish red hydrosulfite vat color. cottonis dyed the same shade, turning to a violet of an excellent fastness,especially to light, when exposed to the air or soaped. In the samemanner the corresponding diethoxyanthanthrone is obtained.

-'We claim 1. A process for producing new anthan throne derivativeswhich process comprises saponifying a naphthostyril-sulfonic acid,corresponding probably to the formula;

to the corresponding l-aminonaphthalene-S- carboxy-mono-sulfonic aciddiazotizing it, treating its diazocomp'ound with reducing agents,converting the formed disulfonic acid derivative of1.1"-dinaphthyl8.8'-dicarboxylic acid by alkali fusion into thecorresponding dihydroxyderivative, subjecting this to the action of acidcondensing agents and treating finally the formed dihydroxyanthanthronewith alkylating agents.

2. As new compounds dialkoxyanthauthrones corresponding probably to thegen eral formula:

which compounds are when dry violet powders, soluble in concentratedsulfurlc acid withv a yellowish greencolor, formmg with an alkalinehydrosulfite solution a bluish red vat,

dyeing cotton therefrom the same shades, turning to a violet of anexcellent fastness especially to light, when exposed to the air orsoaped, which compounds are substantially identical with productsobtainable by saponifying a naphthostyril-sulfonic acid, correspondingprobably to the formula:

OO-NH $0311 to the correspondingl-aminonaphthalene-fficarboxy-mono-sulfonlc acid diazot zing 1t,treating its diazoconipound w1th reducing agents, converting the formeddisulfonic acid derivative of 1.1-dinaphthyl-8.8-dicarbox ylic acid byalkali fusion into the corresponding dihydroxyderivative, subjectingthis to the action of acid condensing agentsand treating finally theformed dihydroxyanthanthrone with alkylating agents;

3. As a new compound, dimethoXyanthan-' throne corresponding to theformula:

which compound is, when dry, a violet pow-- der, soluble inconcentratedsulfuric acid with a yellowish-green color, forming with an alkalinehydrosulfite solution a bluish-red vat, from which cotton is dyedbluish-red shades of an excellent fastness, especially to light, whenexposed to the air or soaped.

In testimony whereof, we aiiix our signatures. V

RICHARD HERZ. WERNER ZERWECK.

CERTIFICATE OF CORRECTION.

i?atent No. 1,805,912. Granted May 19, test to RICHARD HERZ ET AL.

it is hereby certified that error appears in the printed specificationof the above numbered patent requiring correctieu as follows: ?age 2,line 27, for the numeral and sign "100" read 1000; and that the saidLetters Patent should be read with this correction therein that the samemay conform to the record of the ease in the Patent Office.

Signed and sealed this 11th day of August, A. D. 1931.

Wm. A. Kinnan, (Seal) Acting Commissioner of Patents.

